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Is it Possible to Grow Thin Films of Phase Pure Kesterite Semiconductor? A ZnSe case study

Published online by Cambridge University Press:  28 August 2013

Phillip J. Dale
Affiliation:
University of Luxembourg, Laboratory for Energy Materials, 41 rue du Brill, L-4422, Belvaux, Luxembourg.
Monika Arasimowicz
Affiliation:
University of Luxembourg, Laboratory for Energy Materials, 41 rue du Brill, L-4422, Belvaux, Luxembourg.
Diego Colombara
Affiliation:
University of Luxembourg, Laboratory for Energy Materials, 41 rue du Brill, L-4422, Belvaux, Luxembourg.
Alexandre Crossay
Affiliation:
University of Luxembourg, Laboratory for Energy Materials, 41 rue du Brill, L-4422, Belvaux, Luxembourg.
Erika Robert
Affiliation:
University of Luxembourg, Laboratory for Energy Materials, 41 rue du Brill, L-4422, Belvaux, Luxembourg.
Aidan A. Taylor
Affiliation:
Physics Department, Durham University, South Road, Durham, DH1 3LE,UK.
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Abstract

The kesterite semiconductor Cu2ZnSnS(e)4 is seen as a suitable absorber layer to replace Cu(In,Ga)Se2 in thin film solar cells, if thin film photovoltaics are to be deployed on the terawatt scale. Currently the best devices, and hence the best kesterite absorber layers are grown away from stoichiometry and are zinc rich and copper poor, presumably leading to the formation of ZnS(e). However, it has been shown that secondary phases present in an absorber layer reduce device performance. If growth in Zn rich conditions seems to be mandatory, then any secondary phases formed should be grown on the surface of the absorber layer so that they may be easily removed by etching. Therefore, it is important to know how and why secondary phases form, and if possible, how to segregate them to the surface of the absorber layer.

Here we show that ZnSe is formed at the initial stages of absorber formation from annealing metal stacks in selenium vapor. Further we demonstrate that the way the precursor metals are distributed on the substrate leads to different absorber layer performances in full devices. The importance of selenium vapor pressure is highlighted in respect to the order of selenisation of the metals, Zn before Cu. Additionally, the importance of selenium and tin selenide vapor pressure during annealing is reviewed with regard to avoiding a decomposition of the Cu2ZnSnSe4 to ZnSe and Cu2Se phases. Regardless of the atmosphere above the absorber, the reaction of the absorber with molybdenum appears unavoidable without the use of a passivation strategy. Counter-intuitively, it is demonstrated that for our absorber layers grown under Zn-rich conditions, removal of the ZnSe is harmful for device performance.

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Articles
Copyright
Copyright © Materials Research Society 2013 

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References

REFERENCES

Todorov, T.K., et al. ., Beyond 11% Efficiency: Characteristics of State-of-the-Art Cu2ZnSn(S, Se)(4) Solar Cells. Advanced Energy Materials, 2013. 3(1): p. 3438.CrossRefGoogle Scholar
Watjen, J.T., et al. ., Direct evidence of current blocking by ZnSe in Cu2ZnSnSe4 solar cells. Applied Physics Letters, 2012. 100(17).Google Scholar
Tanaka, T., et al. ., Existence and removal of Cu2Se second phase in coevaporated Cu2ZnSnSe4 thin films. Journal of Applied Physics, 2012. 111(5).CrossRefGoogle Scholar
Mousel, M., et al. ., HCl and Br2-MeOH etching of Cu2ZnSnSe4 polycrystalline absorbers. Thin Solid Films, (0).Google Scholar
Berg, D.M., et al. ., Thin film solar cells based on the ternary compound Cu2SnS3. Thin Solid Films, 2012. 520(19): p. 62916294.CrossRefGoogle Scholar
Dudchak, I.V. and Piskach, L.V., Phase equilibria in the Cu2SnSe3-SnSe2-ZnSe system. Journal of Alloys and Compounds, 2003. 351(1-2): p. 145150.CrossRefGoogle Scholar
Lafond, A., et al. ., Crystal Structures of Photovoltaic Chalcogenides, an Intricate Puzzle to Solve: the Cases of CIGSe and CZTS Materials. Zeitschrift Fur Anorganische Und Allgemeine Chemie, 2012. 638(15): p. 25712577.CrossRefGoogle Scholar
Olekseyuk, I.D., Dudchak, I.V., and Piskach, L.V., Phase equilibria in the CU2S-ZnSSnS2 system. Journal of Alloys and Compounds, 2004. 368(1-2): p. 135143.CrossRefGoogle Scholar
Repins, I., et al. ., Co-evaporated Cu2ZnSnSe4 films and devices. Solar Energy Materials and Solar Cells, 2012. 101: p. 154159.CrossRefGoogle Scholar
Barkhouse, D.A.R., et al. ., Device characteristics of a 10.1% hydrazine-processed Cu2ZnSn(Se, S)4 solar cell. Progress in Photovoltaics, 2012. 20(1): p. 611.CrossRefGoogle Scholar
Siebentritt, S., Why are kesterite solar cells not 20% efficient? Thin Solid Films, (0).Google Scholar
Scragg, J.J., Berg, D.M., and Dale, P.J., A 3.2% efficient Kesterite device from electrodeposited stacked elemental layers. Journal of Electroanalytical Chemistry, 2010. 646(1-2): p. 5259.CrossRefGoogle Scholar
Arasimowicz, M., Thevenin, M., and Dale, P.J.. The effect of soft pre-annealing of differently stacked Cu-Sn-Zn precursors on the quality of Cu2ZnSnSe4 absorbers. in Materials Research Society Spring Meeting. 2013. San Francisco: MRS.Google Scholar
Redinger, A., et al. ., The Consequences of Kesterite Equilibria for Efficient Solar Cells. Journal of the American Chemical Society, 2011. 133(10): p. 33203323.CrossRefGoogle ScholarPubMed
Chou, C.Y. and Chen, S.W., Phase equilibria of the Sn-Zn-Cu ternary system. Acta Materialia, 2006. 54(9): p. 23932400.CrossRefGoogle Scholar
Arasimowicz, M., et al. ., Elucidation of the Kesterite Semiconductor Formation Mechanism from Metal Stacks and the Effect of Annealing Parameters. submitted, 2013.Google Scholar
Hergert, F., et al. ., A crystallographic description of experimentally identified formation reactions of Cu(In, Ga)Se-2. Journal of Solid State Chemistry, 2006. 179(8): p. 23942415.CrossRefGoogle Scholar
Schwarz, T., et al. ., Atom probe study of Cu2ZnSnSe4 thin-films prepared by coevaporation and post-deposition annealing. Applied Physics Letters, 2013. 102(4).CrossRefGoogle Scholar
Redinger, A., et al. . Route towards high efficiency single phase Cu2ZnSn(S, Se)4 thin film solar cells: Model experiments and literature review. in Photovoltaic Specialists Conference (PVSC), 2011 37th IEEE. 2011.CrossRefGoogle Scholar
Islam, M.M., et al. ., Impact of Se flux on the defect formation in polycrystalline Cu(In, Ga)Se-2 thin films grown by three stage evaporation process. Journal of Applied Physics, 2013. 113(6).CrossRefGoogle Scholar
Hsu, W.-C., et al. ., Reaction pathways for the formation of Cu2ZnSn(Se, S)(4) absorber materials from liquid-phase hydrazine-based precursor inks. Energy & Environmental Science, 2012. 5(9): p. 85648571.CrossRefGoogle Scholar
Scragg, J.J., et al. ., Thermodynamic Aspects of the Synthesis of Thin-Film Materials for Solar Cells. Chemphyschem, 2012. 13(12): p. 30353046.CrossRefGoogle ScholarPubMed
Scragg, J.J., et al. ., A Detrimental Reaction at the Molybdenum Back Contact in Cu2ZnSn(S, Se)(4) Thin-Film Solar Cells. Journal of the American Chemical Society, 2012. 134(47): p. 1933019333.CrossRefGoogle ScholarPubMed
Shin, B., et al. ., Control of an interfacial MoSe2 layer in Cu2ZnSnSe4 thin film solar cells: 8.9% power conversion efficiency with a TiN diffusion barrier. Applied Physics Letters, 2012. 101(5).CrossRefGoogle Scholar
Guetay, L., et al. ., Lone conduction band in Cu2ZnSnSe4. Applied Physics Letters, 2012. 100(10).Google Scholar
Cummings, C.Y., et al. ., CuInSe2 precursor films electro-deposited directly onto MoSe2. Journal of Electroanalytical Chemistry, 2010. 645(1): p. 1621.CrossRefGoogle Scholar
Schorr, S., et al. ., The complex material properties of chalcopyrite and kesterite thin-film solar cell absorbers tackled by synchrotron-based analytics. Progress in Photovoltaics, 2012. 20(5): p. 557567.CrossRefGoogle Scholar
Just, J., et al. ., Determination of secondary phases in kesterite Cu2ZnSnS4 thin films by xray absorption near edge structure analysis. Applied Physics Letters, 2011. 99(26).CrossRefGoogle Scholar
Fontane, X., et al. ., In-depth resolved Raman scattering analysis for the identification of secondary phases: Characterization of Cu2ZnSnS4 layers for solar cell applications. Applied Physics Letters, 2011. 98(18).CrossRefGoogle Scholar
Djemour, R., et al. ., Detecting ZnSe secondary phase in Cu2ZnSnSe4 by room temperature photoluminescence. Applied Physics Letters, 2013. accepted.CrossRefGoogle Scholar
Watjen, J.T., et al. ., Cu out-diffusion in kesterites-A transmission electron microscopy specimen preparation artifact. Applied Physics Letters, 2013. 102(5).Google Scholar
Vora, N., et al. ., Phase identification and control of thin films deposited by co-evaporation of elemental Cu, Zn, Sn, and Se. Journal of Vacuum Science & Technology A, 2012. 30(5).CrossRefGoogle Scholar
Redinger, A., et al. ., Detection of a ZnSe secondary phase in coevaporated Cu2ZnSnSe4 thin films. Applied Physics Letters, 2011. 98(10).CrossRefGoogle Scholar
Boscher, N.D., et al. ., Atmospheric pressure chemical vapour deposition of SnSe and SnSe2 thin films on glass. Thin Solid Films, 2008. 516(15): p. 47504757.CrossRefGoogle Scholar